阅读说明：本技术 一种环保防腐的建筑陶瓷材料及其制备方法 (Environment-friendly anticorrosive building ceramic material and preparation method thereof ) 是由 陈杰明 于 2020-06-03 设计创作，主要内容包括：本发明公开一种环保防腐的建筑陶瓷材料及其制备方法,该陶瓷材料包括相互贴合的结构层与功能层以及设置在功能层与结构层相背一面上的釉面层；本发明通过设置层状的建筑陶瓷材料结构,能够提升建筑陶瓷材料的抗裂能力,并且在孔隙度较大的功能层中填充无机相变材料,使建筑陶瓷材料具有良好的保温能力,孔隙度较小的结构层中,流体的流动受到限制,限制了腐蚀性流体的流动,提升了建筑陶瓷材料的耐腐蚀效果；本发明结构层原料粒子与功能层原料粒子在制备过程中,将氧化锰以及硝酸盐以溶液的形式通过浸渍的方式进入原料粒子的微孔结构中,从而使氧化物均匀的分散在原料粒子中,提升陶瓷微孔结构的均匀性,从而提升陶瓷材料的力学性质。(The invention discloses an environment-friendly anticorrosive building ceramic material and a preparation method thereof, wherein the ceramic material comprises a structural layer and a functional layer which are mutually attached and a glaze layer arranged on the surface of the functional layer opposite to the structural layer; according to the invention, by arranging the layered structure of the building ceramic material, the crack resistance of the building ceramic material can be improved, and the functional layer with larger porosity is filled with the inorganic phase change material, so that the building ceramic material has good heat preservation capability, and in the structural layer with smaller porosity, the flow of fluid is limited, the flow of corrosive fluid is limited, and the corrosion resistance effect of the building ceramic material is improved; in the preparation process of the structural layer raw material particles and the functional layer raw material particles, manganese oxide and nitrate enter the microporous structure of the raw material particles in a form of solution in a dipping mode, so that oxides are uniformly dispersed in the raw material particles, the uniformity of the microporous structure of the ceramic is improved, and the mechanical property of the ceramic material is improved.)

1. An environment-friendly and corrosion-resistant architectural ceramic material is characterized by comprising a structural layer and a functional layer which are mutually attached and a glaze layer arranged on the back surface of the functional layer opposite to the structural layer, wherein the porosity of the structural layer is 45% -60%, and the porosity of the functional layer is 68% -80%;

the preparation method of the environment-friendly and corrosion-resistant building ceramic material specifically comprises the following steps:

step one, preparing structural layer raw material particles and functional layer raw material particles;

step two, respectively adding the structural layer raw material particles and the functional layer raw material particles into a mold for molding, presintering for 10-13min at the temperature of 240-260 ℃ in a nitrogen atmosphere, and cooling to 25-60 ℃ to obtain a structural layer intermediate and a functional layer intermediate for later use;

coating one surface of the structural layer intermediate with a layer of mixed glue solution, stacking the functional layer intermediate on the layer coated with the mixed glue solution, glazing one surface of the functional layer intermediate opposite to the structural layer intermediate, raising the temperature to 300-400 ℃ at a heating rate of 2 ℃/min under a nitrogen environment, then roasting at a heat preservation time of 10-15min, raising the temperature to 800-1200 ℃ and sintering for 35-60min to obtain a layered material;

completely soaking the layered material obtained in the previous step in a liquid inorganic phase change material, heating the inorganic phase change material to 40-45 ℃, and preserving heat; and (3) vacuumizing, namely pumping out gas in pores of the functional layer, then increasing the pressure in the impregnation liquid pool to 1-7Mpa, taking out the layered material after 24-72 hours, reducing the temperature to 0-10 ℃, and sealing the side surface of the functional layer by using waterproof sealant to obtain the environment-friendly and anticorrosive building ceramic material.

2. The environment-friendly corrosion-resistant architectural ceramic material according to claim 1, wherein the environment-friendly corrosion-resistant architectural ceramic material comprises two structural layers (1) and a functional layer (2) sandwiched between the two structural layers (1), the functional layer (2) comprises a central germ layer (21) and edge sealing germ layers (22) attached to two opposite side faces of the central germ layer (21), the thickness of the edge sealing germ layers (22) is not less than that of the central germ layer, and the structural layer (1) and the edge sealing germ layers (22) are made of the same material.

3. The environment-friendly corrosion-resistant architectural ceramic material as claimed in claim 1, wherein the preparation method of the mixed glue solution comprises the following steps:

adding polyvinyl alcohol into deionized water, heating the deionized water to 95-98 ℃, stirring to completely dissolve the polyvinyl alcohol, adding graphite powder, nano-alumina, nano-silica and nano-calcium oxide, and uniformly dispersing to obtain a mixed glue solution, wherein the mixture of the graphite powder, the nano-alumina, the nano-silica and the nano-calcium oxide accounts for 35-40% of the total weight of the system, the polyvinyl alcohol accounts for 12-20% of the total weight of the system, and the balance is the deionized water, wherein the weight percentages of the components in the mixture of the graphite powder, the nano-alumina, the nano-silica and the nano-calcium oxide are 45%, 15%, 20% and 15%.

4. The environment-friendly corrosion-resistant architectural ceramic material as claimed in claim 1, wherein the structural layer raw material particles are prepared by processing the following raw materials in parts by weight:

35-45 parts of silicon carbide, 2-2.5 parts of polyvinyl alcohol, 10-17 parts of clay, 4-5 parts of foaming agent, 3-4 parts of talcum and 12-13 parts of dolomite, wherein the particle size of each material is 3-7 mu m;

the preparation method of the raw material particles of the structural layer comprises the following steps:

s1, mixing silicon carbide, clay, talc, a foaming agent and dolomite according to the weight parts, adding the mixture into a ball mill, and ball-milling for 1-3 hours to obtain a solid mixture;

s2, adding the solid mixture obtained in the step into a sand mill, adding a foaming agent and polyvinyl alcohol into the mixture, and performing sand milling for 1-3 hours to obtain mixed slurry;

s3, granulating the mixed slurry obtained in the previous step through a spray granulating agent to obtain spherical secondary aggregation particles;

s4, preparing an impregnation liquid with a mass concentration of 7% -20%, wherein the solute is manganese oxide and nitrate, the mass ratio of the manganese oxide to the nitrate is 1: 2.5-3.5, the nitrate is one of aluminum nitrate, calcium nitrate and magnesium nitrate, the solvent is a mixed liquid of deionized water and tetrahydrofuran, and the volume ratio of the deionized water to the tetrahydrofuran is 2-4: 1;

s5, completely immersing the secondary aggregation particles obtained in the step S3 in an impregnation liquid, vacuumizing an impregnation liquid container, increasing the pressure in the impregnation liquid container to 1-7Mpa, taking out the secondary aggregation particles after 3-48 hours, drying for 1-24 hours at 60 ℃ under a negative pressure condition, increasing the drying temperature to 90 ℃, and continuously drying until free water in pores of the secondary aggregation particles is completely discharged;

s6, raising the temperature of the secondary aggregation particles obtained in the previous step to 150-200 ℃ according to the heating rate of 1 ℃/min in a nitrogen atmosphere, and then carrying out heat preservation roasting for 20-60min to decompose the nitrate, so as to obtain the structural layer raw material particles.

5. The environment-friendly corrosion-resistant architectural ceramic material as claimed in claim 1, wherein the functional layer raw material particles are prepared by processing the following raw materials in parts by weight:

35-45 parts of silicon carbide, 2-2.5 parts of polyvinyl alcohol, 10-17 parts of clay, 11-14 parts of foaming agent, 3-4 parts of talc and 6-7 parts of dolomite, wherein the particle size of each material is 3-7 mu m;

the preparation method of the functional layer raw material particles is the same as that of the structural layer raw material particles.

6. The environment-friendly corrosion-resistant architectural ceramic material of claim 1, wherein the foaming agent is one or a mixture of at least two of calcium carbonate, calcium hydroxide and aluminum sulfate.

7. The environment-friendly corrosion-resistant architectural ceramic material as claimed in claim 1, wherein the inorganic phase change material is prepared by processing the following raw materials in parts by weight:

40-50 parts of sodium sulfate decahydrate, 0.2-2 parts of sodium carboxymethylcellulose, 7-12 parts of deionized water, 0.2-0.4 part of sodium bicarbonate and 4-7 parts of silicon micropowder;

the specific preparation method of the inorganic phase-change material comprises the following steps:

and adding a buffering agent into deionized water for dissolving, adding sodium sulfate decahydrate, sodium carboxymethylcellulose and silicon micropowder, and mixing and stirring uniformly to obtain the inorganic phase-change material.

Technical Field

The invention belongs to the technical field of building materials, and particularly relates to an environment-friendly and anticorrosive building ceramic material and a preparation method thereof.

Background

The building material is a material used in a large range and a large scale, can play the functions of heat preservation, water resistance, sun protection and the like and the decorative effect, and along with the environmental awareness of people and the improvement of the requirement on living environment, people seek more excellent building materials to meet the requirement, the ceramic building material is a novel building material, the ceramic building material is a common and popular building material at present due to the characteristics of high temperature resistance, acid and alkali resistance and high strength, and the ceramic building material is often subjected to foaming treatment in the prior art to have a good pore structure, so that the obtained ceramic building material has a good heat insulation effect, but in order to improve the heat insulation performance of the ceramic building material, the ceramic building material needs to be ensured to have larger thickness and foaming effect when being processed, this again takes up a lot of building space and increases the weight of the single piece of ceramic building material.

And the abundant microporous structure causes the ceramic material when in actual use, in corrosive environment, corrosive gas or liquid is easy to enter through the microporous structure of the ceramic, and the porous structure of the ceramic provides a great contact area for the ceramic building material and corrosive fluid, thereby accelerating the corrosion of the ceramic building material, and along with the increase of the pores of the ceramic material, the contact area between the ceramic material and the corrosive gas is larger, which accelerates the corrosion of the ceramic building material, and reduces the pores, which in turn reduces the heat preservation effect of the ceramic material.

Disclosure of Invention

The invention aims to provide an environment-friendly and corrosion-resistant building ceramic material and a preparation method thereof.

The technical problems to be solved by the invention are as follows:

1. in the prior art, in order to ensure that a ceramic material has a good heat-insulating effect, the ceramic material is generally made to have a larger thickness, which also directly improves the production cost and the weight of the ceramic building material, and how to reduce the thickness and the weight of a single ceramic building material without affecting the heat-insulating effect is a problem to be solved at present;

2. due to the porous structure of the ceramic building material, in a corrosive environment, corrosive gas or liquid easily enters through the microporous structure of the ceramic, and the porous structure of the ceramic provides a large contact area for the ceramic building material and corrosive fluid, so that the corrosion of the ceramic building material is accelerated, and how to reduce the corrosion of the ceramic material is one of the problems to be solved at present.

The purpose of the invention can be realized by the following technical scheme:

an environment-friendly and corrosion-resistant architectural ceramic material comprises a structural layer and a functional layer which are mutually attached and a glaze layer arranged on the back surface of the functional layer opposite to the structural layer, wherein the porosity of the structural layer is 45% -60%, and the porosity of the functional layer is 68% -80%;

the preparation method of the environment-friendly and corrosion-resistant building ceramic material specifically comprises the following steps:

step one, preparing structural layer raw material particles and functional layer raw material particles;

step two, respectively adding the structural layer raw material particles and the functional layer raw material particles into a mold for molding, then presintering for 10-13min at the temperature of 240-260 ℃ in a nitrogen atmosphere, cooling to 25-60 ℃ to obtain a structural layer intermediate and a functional layer intermediate for later use, and bonding the materials together for shaping through polyvinyl alcohol bonding so as to facilitate the next operation;

coating one surface of the structural layer intermediate with a layer of mixed glue solution, stacking the functional layer intermediate on the layer coated with the mixed glue solution, glazing one surface of the functional layer intermediate opposite to the structural layer intermediate, raising the temperature to 300-400 ℃ at a heating rate of 2 ℃/min under a nitrogen environment, then roasting at a heat preservation time of 10-15min, raising the temperature to 800-1200 ℃ and sintering for 35-60min to obtain a layered material;

completely soaking the layered material obtained in the last step in a liquid inorganic phase change material, heating the inorganic phase change material to 40-45 ℃, preserving heat, reducing the viscosity of the inorganic phase change material, improving the fluidity of the inorganic phase change material, and accelerating the inorganic phase change material to enter a functional layer; vacuumizing, pumping out gas in pores of the functional layer, increasing the pressure in the impregnation liquid pool to 1-7Mpa, accelerating the impregnation liquid to enter the pores of the secondary aggregation particles, taking out the layered material after 24-72h, reducing the temperature to 0-10 ℃, the side surface of the functional layer is sealed by waterproof sealant to obtain the environment-friendly and anticorrosive building ceramic material, in the step, because the porosity of the structural layer is smaller and the surface agent of the pores is smaller, the inorganic phase-change material has larger resistance to fluid, so that the amount of the inorganic phase-change material entering the structural layer is smaller after the functional layer is completely immersed, as a further scheme of the invention, before the layered material is completely immersed in the inorganic phase-change material, and sealing the structural layer, wherein the material subjected to sealing treatment does not dissolve the inorganic phase change material and does not react with the inorganic phase change material.

The functional layer has larger porosity, so the strength of the functional layer is reduced, the functional layer can be safely used in places with low strength requirements, but when the functional layer is used in places with higher surface strength requirements, the surface of the functional layer is easy to crack when being impacted, and in order to deal with the situation, the structure of the environment-friendly and corrosion-resistant architectural ceramic material can be improved as follows:

the utility model provides an anticorrosive architectural ceramic material of environmental protection, includes two-layer structural layer and the functional layer of clamp between two-layer structural layer, the functional layer includes central germinal layer, with the banding germinal layer of laminating of two opposite sides of central germinal, and the germinal thickness of banding is not less than the germinal thickness of central germinal layer, the structural layer is the same kind of material with the banding germinal layer, and the banding germinal layer plays the supporting role, and the functional layer is the same with above-mentioned method with the combination method of structural layer.

The preparation method of the mixed glue solution comprises the following steps:

adding polyvinyl alcohol into deionized water, heating the deionized water to 95-98 ℃, stirring to completely dissolve the polyvinyl alcohol, adding graphite powder, nano-alumina, nano-silica and nano-calcium oxide into the deionized water, and uniformly dispersing to obtain a mixed glue solution, wherein the mixture of the graphite powder, the nano-alumina, the nano-silica and the nano-calcium oxide accounts for 35-40% of the total weight of the system, the polyvinyl alcohol accounts for 12-20% of the total weight of the system, and the balance is the deionized water, wherein the weight percentages of the components in the mixture of the graphite powder, the nano-alumina, the nano-silica and the nano-calcium oxide are 45%, 15%, 20% and 15%;

upon sintering, CaO-Al is formed₂O₃-SiO₂And sintering and bonding the structural layer and the functional layer together.

The structural layer raw material particles are prepared by processing the following raw materials in parts by weight:

35-45 parts of silicon carbide, 2-2.5 parts of polyvinyl alcohol, 10-17 parts of clay, 4-5 parts of foaming agent, 3-4 parts of talcum and 12-13 parts of dolomite, wherein the particle size of each material is 3-7 mu m;

the preparation method of the raw material particles of the structural layer comprises the following steps:

s1, mixing silicon carbide, clay, talc, a foaming agent and dolomite according to the weight parts, adding the mixture into a ball mill, and ball-milling for 1-3 hours to obtain a solid mixture;

s2, adding the solid mixture obtained in the step into a sand mill, adding a foaming agent and polyvinyl alcohol into the mixture, and performing sand milling for 1-3 hours to obtain mixed slurry;

s3, granulating the mixed slurry obtained in the previous step through a spray granulating agent to obtain spherical secondary aggregation particles;

s4, preparing an impregnation liquid with a mass concentration of 7% -20%, wherein the solute is manganese oxide and nitrate, the mass ratio of the manganese oxide to the nitrate is 1: 2.5-3.5, the nitrate is one of aluminum nitrate, calcium nitrate and magnesium nitrate, the solvent is a mixed liquid of deionized water and tetrahydrofuran, and the volume ratio of the deionized water to the tetrahydrofuran is 2-4: 1;

s5, completely immersing the secondary aggregation particles obtained in the step S3 in an impregnation liquid, vacuumizing an impregnation liquid container, pumping out gas in pores of the secondary aggregation particles, increasing the pressure in the impregnation liquid container to 1-7Mpa, accelerating the impregnation liquid to enter the pores of the secondary aggregation particles, taking out the secondary aggregation particles after 3-48 hours, firstly drying for 1-24 hours at 60 ℃ under a negative pressure condition, and then increasing the drying temperature to 90 ℃ to continue drying until free water in the pores of the secondary aggregation particles is completely discharged;

s6, raising the temperature of the secondary aggregation particles obtained in the previous step to 150-200 ℃ according to the heating rate of 1 ℃/min in a nitrogen atmosphere, and then carrying out heat preservation roasting for 20-60min to decompose the nitrate, so as to obtain the structural layer raw material particles.

According to the step, the raw materials are subjected to ball milling, grinding and mixing and then are granulated, so that the mixing effect of the materials is improved, and the manganese oxide and the nitrate are soaked into the secondary aggregation particles in a solution form, so that the combination effect and the uniformity of the manganese oxide, the copper oxide and the like with the secondary aggregation particles are improved, the sintered ceramic is more compact, the flowing capacity of fluid in a structural layer is reduced, and the fluid has better mechanical properties;

the functional layer raw material particles are prepared by processing the following raw materials in parts by weight:

35-45 parts of silicon carbide, 2-2.5 parts of polyvinyl alcohol, 10-17 parts of clay, 11-14 parts of foaming agent, 3-4 parts of talc and 6-7 parts of dolomite, wherein the particle size of each material is 3-7 mu m;

the preparation method of the functional layer raw material particles is the same as that of the structural layer raw material particles.

The foaming agent is one or the mixture of at least two of calcium carbonate, calcium hydroxide and aluminum sulfate;

the inorganic phase-change material is prepared by processing the following raw materials in parts by weight:

40-50 parts of sodium sulfate decahydrate, 0.2-2 parts of sodium carboxymethylcellulose, 7-12 parts of deionized water, 0.2-0.4 part of sodium bicarbonate and 4-7 parts of silicon micropowder;

wherein the silicon micropowder can play a good heat conduction effect and can be used as a crystal nucleus to promote the cooling crystallization of the phase-change material, the buffering agent is sodium bicarbonate and is used for adjusting the viscosity of the phase-change material and preventing the phase-change material from generating severe change of pH value in the process of entering pores of the building ceramic material so as to influence the viscosity of the phase-change material,

the specific preparation method of the phase-change material comprises the following steps:

and adding a buffering agent into deionized water for dissolving, adding sodium sulfate decahydrate, sodium carboxymethylcellulose and silicon micropowder, and mixing and stirring uniformly to obtain the inorganic phase-change material.

The invention has the beneficial effects that:

1. according to the invention, by arranging the layered structure of the architectural ceramic material, on one hand, the crack resistance of the architectural ceramic material can be improved, on the other hand, a structural layer with smaller porosity and more compact structure is used as a layer for providing strength, and the functional layer with larger porosity is filled with the inorganic phase change material, so that the architectural ceramic material has good heat preservation capability, the thickness of the ceramic material can be reduced, and the ceramic material has good heat preservation effect;

2. the invention uses the mixed glue solution as a connecting agent to sinter the structural layer and the functional layer together to form CaO-Al₂O₃-SiO₂The three-dimensional structure of (2) guarantees the connection effect between structural layer and the functional layer, and simultaneously, structural layer raw material particle and functional layer raw material particle are in the preparation process, get into raw material particle's microporous structure with manganese oxide and nitrate through the mode of flooding with the form of solution, turn into the oxide with nitrate through the calcination to make the even dispersion of oxide in raw material particle, promote ceramic microporous structure's homogeneity, thereby promote ceramic material's mechanical properties.

Drawings

The invention is described in further detail below with reference to the figures and specific embodiments;

FIG. 1 is a schematic structural view of an environment-friendly and corrosion-resistant architectural ceramic material in example 2.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.